Halogenated pyridinoanthraquinones



Patented Nov. 28, 1 933 oFFIcE HALOGENATED PYRlDINOANTHRA- QUINONES I Max Albert Kunz, Mannheim, and Karl Koeberleand Gerd Kochendoerfer, Ludwigshafen-on the-Rhine, Germany,

assignors to General Aniline Works, Inc., New York, N. Y.,,a corpp.-'

ration of Delaware No Drawing. Application January 22, 1932,

Serial No. 588,232, and in Germany January 28,

The present invention relates to new compounds which are halogenated pyridinoanthraquinones, and process of producing same. I I a We have found that halogenated pyridinOanthraquinones are obtained by treating pyridino" anthraquinone or its substitution products with chlorine, bromine or iodine or agents supplying these halogens in the absence of any diluent or v in the presence of an inert organic or inorganic diluent, if desired in the presence of halogen transferrers. Suitable organic diluents in which halogenation may be carried out, are in'particulararomatic diluents of highboiling point, such W as nitro and halogen substitution products of benzene and its homologues, naphthalene and its substitution products and the like. Inorganic diluents which may be employed are, for exam ple, Water to which alkalies' may be added, and in particular sulphuric acids, such as sulphuric acid itself in a concentrated and'diluted state,

oleum and chlorosulphonic acid. As halogenat ingcatalysts' those usually employed in halogenations may be used. T l V Thencw halogen substitution products of pyridinoanthraquinones may also be, produced by replacing an amino group or amino groups in amino-pyriclinoanthraquinones' by halogen by way of the diazo compound. The diazotization, may be carried out by the usual methods by means of a nitrate in sulphonic acid or nitrosylsulphuric acioL' Also the replacement of the diazo group or groups by halogen can be carried 7 out by "conventional methods, for example by treating the diazo compounds with cuprous halides or alkali metal iodides. v

A further method of producing the new halogen derivatives of pyridinoanthraquinoneswhich is particularly advantageous 'in View of the uniform productsobtained thereby consists in treating halogenated aminoanthraquinones, in which at least one ortho position to an amino group is unoccupied, with glycerine or its substitution products, as for example. chlorhydrins, or its equivalents, such as their anhydrides, esters and others, in the presence of an oxidizing agent in acid, preferably sulphuric acid, solution at temperatures above 100 C., but generally speaking, below 170 C. The most suitable temperatures are between about 105 and 120 C. Especially uniform products are obtained by thismethod when starting from halogenated aminoanthraquinones in which one ortho position to the amino group is free and the other occupied as is the case with halogenated l-aminoanthraquinones having a free Z-position and Z-aminoan- 130 (3., due to some decomposition of gly'cerine synthetic methodof producing halogenatedpyri- 9 Claims. (01. 260-40) thraquinones having a free .l-position or, 3-position and substituted in the 3-positionor'1-position respectively by halogen, or any other sub- "stituent and containing halogen in addition thereto 'lhebxidizing agent is to be added in at least an equivalent amount, i. e. an amount suficient to yield one atomic proportion of 'oxygen for each pyridino ring to be formed. When" calculating the necessary amount of oxidizing agent, it is to be kept in mind that the mixture of glycerine and sulphuric acid can react as a reducing agent, in particular at higher temperatures, for example at temperatures above about occurring and, thereiorait is necessary to make good for such reducing action by the addition of a surplus of oxidizing agent. I Instead of halogenated aminoanthraquinones themselves, their ll-substitution products, for ex; ample their acylcoinpouiids, or compounds which, are. capable of reacting'as a'minoanthraquinones, for example the corresponding aaomethineamay also be employed as starting materials for the dinoanthraquinones by means of ,a' glycerine finsulphuric acid in the presence. oi-an oxidizing agent. Suitable oxidizing agents are,.for exam: ple, organic nitro compounds, such as picryl chlo-- ride,'nitrobenzene and its sulphonic acids, arsenicl acid and'ierric salts. Halogenated pyridine anthraquinones prepared by the said synthetic method or by way of the diazocompounds may also further be halogenated by direct halogenation in the above describedmanner.

Substituents present inlthe initial materials do not interfere with the aforedescribed methods of producing halogenated, pyridinoanthraquinones. Thus cyano, carboxylic,mereapto, hydroxy, a1-' koxy, nitrdarnino, substitutedfamino,sulpho and pyridino groups may be present in the initial materials.

The halogenated pyridinoanthraquinones and their substitution products are, generally speaking, practically colorless or. slightlyyellow substances which dissolve comparatively readily in concentrated sulphuric acid giving usually yellow to orange red colorationawhile their vat solutions are usually orange to blue in color. The re action products may be purified, either simulta neously with their preparation or subsequently thereto, by the usual methods, as for; example crystallization or boiling with organic solvents, I or by way of their salts withstrong'acids, or by,

sublimation, vatting or treatment with oxidizing; Q

agents.

parts of 2(N)-l-pyridinoanthraquinone are heated to boiling for several hoursin EGQ'parts of trichlorbenaene after the addition of 5 parts of iodine and while leading in chlorine gas. Thereaction proceeds according to theiollowing equation:'

After cooling; the reaction product which'separates in the form of yellow needles is filtered off by suction. According to analysis the product is a monochlor derivative; it dissolves in concentrated sulphuric acid giving an orange coloration and its vat solution is violet;

Starting with 3-cyan-2 (N)--1-pyridinoanthraquinone (obtainable from 3-brom-2 (N)-l-pyri- 'dinoanthraquinone (see Example l) by heating with cuprous cyanide in pyridine) a reaction product containing chlorine which gives a violet blue vat isobtained in a similar manner; in the same way 2 (N) -1-pyridinoanthraquinone-3-carboxylic acid (obtainable from the said oyano derivative by saponification) or 3 -rnercapto-2di) l-pyridinoanthraquino'ne (obtainable from 3- .brom-2(N)-1pyrldinoanthraquinone by boiling with-sodium sulphide) is converted into a'reac, tion product containing chlorine by the treatment. (Starting with 3-methyl-2(N)-1- pyridinoanthraquinone a chloro-3 1nethyl2 (N) 1-pyridinoanthraquinone is obtained in the aforedescribed manner. Byv the same method alsojthe' corresponding phenyl 'derivativesiof halogenated pyridinoanthraquinones are obtained.

Emample 30 parts of "1 chlor-,2'-arninoanthraquincne are dissolved in 400 parts of concentrated sulphuric and then .25 parts of sodiumnitrobenzene sul- CHZOEI l After cooling, the sulphate oi the reaction product which has separated in a orystalline'iorm is Example 3 100 parts of 1(N) -2pyridinoanthraquinoneare.

suspended in 500 parts of' nitrobenzene while stirring. After adding 0.5 part of iodine and 150 parts of sulphuryl chloride, the mixture is heated at 90 to, 100. C. 'for several hours and then allowed to cool. The chlor-1(N)-,2-pyridinoanthraquinone which separates out is filtered ofi by suction. It is a yellow powder, dissolves in concentrated sulphuric acid giving a yellow 5 coloration and yields anorange vat.

Example 4 dissolved in 300 parts of concentrated sulphuric acid and then 17 parts of nitrobenzene sulphonic acid, 20 parts of 90 per centglycerine and 30 parts of water are introduced. The mixture is heated to from 105 to 115 1. for about 1 hours and then 200 parts of water are stirred in. The su1- phateof the reaction product whichseparates out in a crystalline form is filtered off by suction is'recovered therefrom in the usual manner as a yellow powder. It may be crystallized from organic solvents. The color of its solutions in sulphuric acid is yellow while its vat is red having aviolet shade. I I v Example 5 50 parts of 2(N) -3 pyridinoanthraquinone (prepared from 1-chlor-2(N)--3pyridinoanthra quinone as obtained in Example 2 by dehalogenation) are dissolved while stirring in 500 parts of chlorsulphonic acid. After adding 0.5 part of iodine and 50 parts of bromina'the mixture is heated slowly to from 65t0 70 0., kept at this temperature until all. of the bromine has been and the 3- rem-2(N -1-pyridinoanthraquinone consumed, allowed tocool, diluted with a little sulphuric 'acid, poured into ice-water, boiled for a short time andthe reaction product filtered,

off bysuction and dried. The brorn-2(N)-3 pyridinoanthraquinone thus obtained isa strawyellow powder, crystallizes in the form of yellow needles, dissolves in concentrated sulphuric acid giving a green yellow coloration and yields. a yellow green vat.

When starting from mac-2m) -1-pyridinoanthraquinone (obtainable by nitrating 2.(N)'-1-' pyridinoanthraquinonein sulphuric acid with' nitric acid) brorno-nitro-2(N) -l-pyridinoanthra-" quinone is obtained in the aforedescribed manner.. It is a yellow powder yielding a violet vat in an alkaline hydrosulphite solution.

A reaction product containing chlorine and iodine is obtained in ananalogous manner by heating 12 parts .of '1-chlor-2(N)- 3-pyridino-,. ice and the clearayellowbrown solution is stirred;

anthraquinone in1100 parts of monohydrate and 20 parts of oleum with 5 parts of iodine at from 140 to 150 'C. i 1 I Example 6 l I I 50 parts of 8-chlor-1-aminoanthraqulnoneare dissolved in 700 parts of concentrated'sulphu'ric acid, 15 parts of 90 per cent glycerine and 70 parts of water'are introduced. The mixture is heated for from about'1 to 2 hours at from .110 to 120 C., poured into a large amount of water, filtered by suction from small amounts of impurities which have separated and the filtrate rendered alkaline. A yellow brown precipitate separates which is filtered off by suction, washed until neutral and dried. The 8-chlor-1-'(N)-2-' pyridinoanthraquinone thus obtained -may be further purified .by crystallization. It is readily soluble even in dilute acids; the color of its solutions in sulphuric acid is yellow red. In the same way 5-chlor-1 (N) -2-pyridinoanthraquinone may be obtained from 5-chlor-1-aminoanthraquinone, or 4-chlor-1(N) -2-pyridinoanthraquinone from 4-chlor-l-aminoanthraquinone.

In an analogous manner the corresponding bromo derivatives of 1(N) -2-pyridinoanthraquinone are obtained.

Example 7 10 parts of 3-hydroxy-2(N) -1-pyridinoanthraquinone (obtainable from 3-hydroxy-2-aminoanthraquinone by condensation with glycerine in sulphuric acid in the presence of oxidizing agents) are dissolved in about 200 parts .of 2 per cent caustic soda solution. parts of bromine are then added and the whole heated for several hours at from 95 to 100 C., allowedto cool and the reaction product obtained in -ex-' cellent yields filtered off by suction. It is a yellow powder which dissolves in concentrated sulphuric acid giving a golden yellow coloration, in caustic soda solution giving a violet colora-' tion and in alkaline hydrosulphite to give a red brown vat.

By heating 8-chlor-1(N)-2-pyridinoanthraquinone with 3 parts of bromine without employing a diluent but in the presence of 0.05 part of iodine at from to C., a brown red bromochloro derivative is obtained which is converted by treatment with sodium bisulphite solution into a sulphonic acid which dyes wool yellow red shades from acid baths.

Example 8 14 parts of mono-amino-2(N)-l-pyridinoan-' thraquinone (obtainable by ,nitrating 2(N)-1- pyridinoanthraquinone in solution in sulphuric acid and reducing the nitro derivative formed) are dissolved in parts of concentrated sulphuric acid and then the calculated amount of nitrosyl sulphuric acid is added at from 10 to 20 C. After ashort time the whole is poured onto violet. I

An orange colored derivative. is obtained by into an aqueous solution of potassium iodide.

While the solution'froths strongly, a red-brown mass separates which,-after warming the-reacpyridinoanthraquinone thus obtained may be crystallized for example from trichlorbenzene.

The reaction proceeds according to the renew:

ing formulae:

E em r:

parts of 1-chlor-2(N) -3 -pyridinoanthra-" quinone (prepared as described in Example 2) are dissolved in 1000 parts of chlorsulphonic acid, while stirring. After addinglO parts .of 5111- phur, 0.5 part of mercury and 100 parts of bromine the whole is heated at 80 C. until all the bromine has been consumed. The whole is then allowed to cool and is worked up in the usual manner.

The resulting brom-1-chlor-2(N)-3-- pyridinoanthraquinone, a yellowish powder,

crystallizes in the form of pale yellow needles, dissolves in concentrated sulphuric acid giving a yellow green coloration and yields a yellow green vat.

A tribrom-2(N) -1-pyridinoanthraquinone is obtained in a similar manner from 3-brom-'2(N) l-pyridinoanthraquinone. I

Example 10 10 parts of the dipyridinoanthraquinone obtained from 2.G-diaminoanthraquinone by treating with glycerine ad sulphuric acid in the presence of nitrobenzene sulphonic acid are heated for several hours while stirring atfrom 60? to 65 C. in

500 parts of oleum containing 11.5 per cent of free SO: after the addition of 50 parts of bromine.

After cooling the reaction mixture is worked up in the usual manner. The resulting bromdipyridinoanthraquinone is a yellow powder which may be crystallized from organic solvents or from sulphuric acid; it dissolves in the latter giving a golden yellow coloration and its vat solutions are chlorinating in concentrated sulphuric acid solution -methoxy-1 (N) -2-pyridinoanthraquinone (obtainable by treating 1-amino-4-methoxyanvthraquinone with glycerine and sulphuric acid in the. presence of nitrobenzene sulphonic acid).

1 Example 11 l to 115 C. and poured intowate'r. The precipitate is filtered, off by suction and'dried. The reaction product is crystallized from trichlorbenzene; it is a yellow crystal powder and is identiphuric acid to give yellow to orange red solutions.

4. 2(N)-3-pyridinoanthraquinones containing at least one of the halogens chlorine, bromine" and iodine, readily soluble in concentrated sulcalv with the 2(N) -1-pyridino-3bromanthra+" .quinone obtainable accordingto Example 4.

Other esters of glycerine and likewise epichlor hydrin may be employed instead of monoa'cetin.

;What we claim is: 1

1. Pyridinoanthraquinonescontaining atleast one of the halogens chlorine, bromine and iodine,

readily soluble in concentrated sulphuric acid to give yellow to orange-red solutions. 7

2.. 1 (N) -2-pyridinoanthraquinones containing at least one of the halogens chlorine, bromine and iodine, readily soluble in concentrated sulphuric acid to give yellow to orange red solutions;

3.12 (N) -1-pyridinoanthraquinones containing at least one of the halogens chlorine, bromine and iodine, readily. soluble in concentrated sulphuric acid to give yellow to orange red solutions. 5. 1(N) -2-pyridinoanthraquinones containing at least one of the halogens chlorine, bromine M and iodine, forming yellow powders, dissolving'in, concentrated sulphuric acid to give yellow; solua tions and yielding orange solutions in an alkaline.

hydrosulphite solution. e e v 6. 1(N) 2-pyridinoanthraquinonesi containing at least one of the halogens chlorine, bromine and iodine in an alpha position, forming yellow powders, dissolving in concentrated sulphuric acid to give. yellow solutionsand yielding "iorang'e solu tionsin an alkalinehydrosulphite solution. 2 v

' ,7. 1(N)'-2 pyridinoanthraquinones containing. v chlorine, forming yellow powders/dissolving in" concentrated sulphuric acid to give yellow solutions and yielding orange solutions in an alkaline forming al yellow" powder, dissolving in co'ncen trated' sulphuric acid to give a yellow solution and yielding a violet solution inan alkaline hydro sulphit'e solutionf l H 7 AX' LBERT KARL KOEBER'LE. I

1 v GERD- KOCHENDOERFER. 

